Organic electroluminescent materials and devices

ABSTRACT

A compound having a structure of Formula I: 
                         
is provided. In the structure of Formula I, each one of X 1  to X 16  is independently CR X  or N; each R X  and R are independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof; and any adjacent R X  can join to form fused or unfused rings. Formulations and devices, such as an OLEDs, that include the compound containing a structure of Formula I are also described.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Patent Application Ser. No. 62/192,628, filed Jul. 15, 2015, the entire contents of which is incorporated herein by reference.

PARTIES TO A JOINT RESEARCH AGREEMENT

The claimed invention was made by, on behalf of, and/or in connection with one or more of the following parties to a joint university corporation research agreement: The Regents of the University of Michigan, Princeton University, University of Southern California, and the Universal Display Corporation. The agreement was in effect on and before the date the claimed invention was made, and the claimed invention was made as a result of activities undertaken within the scope of the agreement.

FIELD

The present invention relates to compounds for use in devices, such as organic light emitting diodes, including the same.

BACKGROUND

Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.

OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Alternatively the OLED can be designed to emit white light. In conventional liquid crystal displays emission from a white backlight is filtered using absorption filters to produce red, green and blue emission. The same technique can also be used with OLEDs. The white OLED can be either a single EML device or a stack structure. Color may be measured using CIE coordinates, which are well known to the art.

One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy)₃, which has the following structure:

In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.

As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.

As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.

As used herein, “solution processable” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.

A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.

As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.

As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.

More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.

SUMMARY

According to one embodiment, a compound having a structure of Formula I:

is provided. In the structure of Formula I:

each one of X¹ to X¹⁶ is independently CR^(X) or N;

each R^(X) and R are independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof; and

any adjacent R^(X) can join to form fused or unfused rings.

According to another embodiment, a first organic light emitting device is provided. The first organic light emitting device can include an anode; a cathode; and an organic layer disposed between the anode and the cathode. The organic layer can include a compound of Formula I as described herein. The device can be incorporated into a consumer product, an electronic component module, an organic light-emitting device, and/or a lighting panel.

According to yet another embodiment, a formulation containing a compound of Formula I as described herein is provided.

BRIEF DESCRIPTION OP THE DRAWINGS

FIG. 1 shows an organic light emitting device.

FIG. 2 shows an inverted organic light emitting device that does not have a separate electron transport layer.

FIGS. 3 & 4 are tables summarizing photophysic and electrochemistry data for selected compounds of Formula I.

DETAILED DESCRIPTION

Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.

The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.

More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.

FIG. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference.

More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F₄-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an “inverted” OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. FIG. 2 provides one example of how some layers may be omitted from the structure of device 100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to FIGS. 1 and 2.

Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in FIGS. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Forrest et al., and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated by reference in their entireties.

Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and OVJD. Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processability than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.

Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.

Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cell phones, tablets, phablets, personal digital assistants (PDAs), wearable device, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicles, a large area wall, theater or stadium screen, or a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.), but could be used outside this temperature range, for example, from −40 degree C. to +80 degree C.

The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.

The term “halo,” “halogen,” or “halide” as used herein includes fluorine, chlorine, bromine, and iodine.

The term “alkyl” as used herein contemplates both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group may be optionally substituted.

The term “cycloalkyl” as used herein contemplates cyclic alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 10 ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, and the like. Additionally, the cycloalkyl group may be optionally substituted.

The term “alkenyl” as used herein contemplates both straight and branched chain alkene radicals. Preferred alkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl group may be optionally substituted.

The term “alkynyl” as used herein contemplates both straight and branched chain alkyne radicals. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted.

The terms “aralkyl” or “arylalkyl” as used herein are used interchangeably and contemplate an alkyl group that has as a substituent an aromatic group. Additionally, the aralkyl group may be optionally substituted.

The term “heterocyclic group” as used herein contemplates aromatic and non-aromatic cyclic radicals. Hetero-aromatic cyclic radicals also means heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperdino, pyrrolidino, and the like, and cyclic ethers, such as tetrahydrofuran, tetrahydropyran, and the like. Additionally, the heterocyclic group may be optionally substituted.

The term “aryl” or “aromatic group” as used herein contemplates single-ring groups and polycyclic ring systems. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is aromatic, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Especially preferred is an aryl group having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may be optionally substituted.

The term “heteroaryl” as used herein contemplates single-ring hetero-aromatic groups that may include from one to five heteroatoms. The term heteroaryl also includes polycyclic hetero-aromatic systems having two or more rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted.

The alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl may be unsubstituted or may be substituted with one or more substituents selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

As used herein, “substituted” indicates that a substituent other than H is bonded to the relevant position, such as carbon. Thus, for example, where R¹ is mono-substituted, then one R¹ must be other than H. Similarly, where R¹ is di-substituted, then two of R¹ must be other than H. Similarly, where R¹ is unsubstituted, R¹ is hydrogen for all available positions.

The “aza” designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C—H groups in the respective fragment can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.

It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.

Tetrabenzoazonine has a unique saddle-shaped structure in which all the phenyl groups are orientated above and below the average plane of the molecule and have minimum conjugation. With this distinct structure, it has been discovered that tetrabenzoazonine is very useful as a high triplet N-containing building block for many applications, e.g., OLED materials.

According to one embodiment, a compound having a structure of Formula I:

Formula I is described. In the structure of Formula I:

each one of X¹ to X¹⁶ is independently CR^(X) or N;

each R^(X) and R are independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof; and

any adjacent R^(X) can join to form fused or unfused rings.

In some embodiments, the compound has the structure of Formula I-a:

Formula I-a. In the structure of Formula I-a:

each one of R¹ to R¹⁶ independently represents a substituent selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof,

any adjacent R¹-R¹⁶ can join to form a fused or unfused ring.

In some embodiment, the compound has a structure of Formula II:

Formula II. In the structure of Formula II,

n is an integer≥1;

R^(t) is

all rings are optionally independently substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof; and

any adjacent substituents can join to form fused or unfused rings.

In some embodiments, compounds of Formula II are selected from the group consisting of

where all of the rings are optionally substituted. In some such embodiments, none of the rings of Compounds II-1 through II-6 are substituted. In some such embodiments, one or more rings of Compounds II-1 through II-6 are independently substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof; where any adjacent substituents can join to form fused or unfused rings.

In some embodiments, R is selected from the group consisting of aryl, heteroaryl, substituted aryl, and substituted heteroaryl. In some such embodiments, the compound is selected from the group consisting of:

where all of the rings are optionally substituted. In some such embodiments, none of the rings of Compounds III-a-1 through III-a-23 are substituted. In some such embodiments, one or more rings of Compounds III-a-1 through III-a-23 are independently substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof; where any adjacent substituents can join to form fused or unfused rings.

In some embodiments, a compound of Formula I-a is disclosed where at least one of R¹ to R¹⁶ is selected from the group consisting of aryl, heteroaryl, substituted aryl, and substituted heteroaryl. In some such embodiments, the compound is selected from the group consisting of:

where all of the rings are optionally substituted. In some such embodiments, none of the rings of Compounds III-1b-1 through III-b-18 are substituted. In some such embodiments, one or more rings of Compounds III-b-1 through III-b-18 are independently substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, axatriphenylene, and combinations thereof: where any adjacent substituents can join to form fused or unfused rings.

In some embodiments, a compound of Formula I-a is described where R is a triarylamine containing group (i.e. a substituent containing a triarylamine group). In some such embodiments, the compound is selected from the group consisting of:

where all of the rings are optionally substituted. In some such embodiments, none of the rings of Compounds IV-1 through IV-4 are substituted. In some such embodiments, one or more rings of Compounds IV-1 through IV-4 are independently substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof; where any adjacent substituents can join to form fused or unfused rings.

In some embodiments, a compound of Formula I-a is described where R is a group containing at least one electron withdrawing group of CN, F, C_(m)F_(2m+1), Si_(m)F_(2m+1), NCO, NCS, OCN, SCN, OC_(m)F_(2m+1), or SC_(m)F_(2m+1), wherein m≥1. In some such embodiments, the compound is selected from the group consisting of

where R^(e) is CN, F, C_(m)F_(2m+1), Si_(m)F_(2m+1), NCO, NCS, OCN, SCN, OC_(m)F_(2m+1), or SC_(m)F_(2m+1), and m≥1; and where R^(t) is

In one embodiment, R^(e) is CN. In such an embodiment, the compound is selected from the group consisting of:

In these embodiments, all rings of R^(t) are optionally independently substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof; and any adjacent substituents on R^(t) can join to form fused or unfused rings.

In some embodiments, a compound of Formula I-a is described where R is a group containing pyrimidine or triazene. In some such embodiments, the compound is selected from the group consisting of:

where R^(t) is

In some such embodiments, all rings of R^(t) are optionally independently substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof; and any adjacent substituents on R^(t) can join to form fused or unfused rings.

In some embodiments, at least one of X¹ to X¹⁶ is N. In some such embodiments, the compound is selected from the group consisting of:

where all of the rings are optionally substituted. In some such embodiments, none of the rings of Compounds VII-1 through VII-14 are substituted. In some such embodiments, one or more rings of Compounds VII-1 through VII-14 are independently substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof; where any adjacent substituents can join to form fused or unfused rings.

In some embodiments, at least two of adjacent R¹-R¹⁵ are fused into or

where Z is CR′R″, NR′, O, S, or Se. In such embodiments, R′ and R″ are independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof; and all of the rings are optionally substituted. In some such embodiments, the compound is selected from the group consisting of:

wherein all of the rings are optionally substituted. In some such embodiments, none of the rings of Compounds VIII-1 through VIII-22 are substituted. In some such embodiments, one or more rings of Compounds VIII-1 through VIII-22 are independently substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof; where any adjacent substituents can join to form fused or unfused rings.

According to another embodiment, a first organic light emitting device is described. The first organic light emitting device can include an anode; a cathode; and an organic layer disposed between the anode and the cathode. The organic layer can include a compound having the structure of Formula I, and its variants, as described herein.

In some embodiments, the organic layer is an emissive layer and the compound of Formula I is a host.

In some embodiments, the organic layer also includes a phosphorescent emissive dopant wherein the phosphorescent emissive dopant is a transition metal complex having at least one ligand or part of the ligand if the ligand is more than bidentate, selected from the group consisting of:

In the structures of the ligands:

each X¹ to X¹³ are independently selected from the group consisting of carbon and nitrogen;

X is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″;

R′ and R″ are optionally fused or joined to form a ring;

each R_(a), R_(b), R_(c), and R_(d) may represent from mono substitution to the possible maximum number of substitution, or no substitution;

R′, R″, R_(a), R_(b), R_(c), and R_(d) are each independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and

any two adjacent substituents of R_(a), R_(b), R_(c), and R_(d) are optionally fused or joined to form a ring or form a multidentate ligand.

In some embodiments, the organic layer is a charge carrier blocking layer and the compound of Formula I is a charge carrier blocking material in the organic layer.

In some embodiments, the organic layer is a charge carrier transporting layer and the compound of Formula I is a charge carrier transporting material in the organic layer.

In some embodiments, the first organic light emitting device is incorporated into a device selected from the group consisting of a consumer product, an electronic component module, an organic light-emitting device, and a lighting panel.

In some embodiments, the organic layer is an emissive layer and the compound having structure according to Formula I is a first light emitting compound. In some such embodiments, the first organic light emitting device emits a luminescent radiation at room temperature when a voltage is applied across the organic light emitting device, and the luminescent radiation comprises a delayed fluorescence process. In some such embodiments, the emissive layer further comprises a first phosphorescent emitting material. In some such embodiments, the emissive layer further comprises a second phosphorescent emitting material. In some such embodiments, the emissive layer further comprises a host material.

In some embodiments, where the compound of Formula I is a first light emitting compound, the first organic light emitting device emits a white light at room temperature when a voltage is applied across the organic light emitting device. In some such embodiments, the first light emitting compound emits a blue light with a peak wavelength of about 400 nm to about 500 nm, while the first light emitting compound emits a yellow light with a peak wavelength of about 530 nm to about 580 nm in other embodiments. In some embodiments, a second organic light emitting device can be stacked on the first organic light emitting device.

The OLED can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel.

In yet another aspect of the present disclosure, a formulation that comprises the first compound of the present disclosure is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, and an electron transport layer material, disclosed herein.

Combination with Other Materials

The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.

Conductivity Dopants:

A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer.

Non-limiting examples of the conductivity dopants that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO006081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804 and US2012146012.

HIL/HTL:

A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoO_(x); a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.

Examples of aromatic amine derivatives used in HIL or HTL include, but are not limited to the following general structures:

Each of Ar¹ to Ar⁹ is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each Ar may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, Ar¹ to Ar⁹ is independently selected from the group consisting of:

wherein k is an integer from 1 to 20; X¹⁰¹ to X¹⁰⁸ is C (including CH) or N; Z¹⁰¹ is NAr¹, O, or S; Ar¹ has the same group defined above.

Examples of metal complexes used in HIL or HTL include, but are not limited to the following general formula:

wherein Met is a metal, which can have an atomic weight greater than 40; (Y¹⁰¹-Y¹⁰²) is a bidentate ligand, Y¹⁰¹ and Y¹⁰² are independently selected from C, N, O, P, and S; L¹⁰¹ is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.

In one aspect, (Y¹⁰¹-Y¹⁰²) is a 2-phenylpyridine derivative. In another aspect, (Y¹⁰¹-Y¹⁰²) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc⁺/Fc couple less than about 0.6 V.

Non-limiting examples of the HIL and HTL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN102702075, DE 102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, U.S. Ser. No. 06/517,957, US20020158242, US20030162053, US20050123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US2011007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, U.S. Pat. No. 5,061,569, U.S. Pat. No. 5,639,914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO2013087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018,

EBL:

An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.

Additional Hosts:

The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting dopant material, and may contain one or more additional host materials using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria is satisfied.

Examples of metal complexes used as host are preferred to have the following general formula:

wherein Met is a metal; (Y¹⁰³-Y¹⁰⁴) is a bidentate ligand, Y¹⁰³ and Y¹⁰⁴ are independently selected from C, N, O, P, and S; L¹⁰¹ is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.

In one aspect, the metal complexes are:

wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.

In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y¹⁰³-Y¹⁰⁴) is a carbene ligand.

Examples of other organic compounds used as additional host are selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; group consisting aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothlenopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and group consisting 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Wherein each group is further substituted by a substituent selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrite, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, host compound contains at least one of the following groups in the molecule:

wherein R¹⁰¹ to R¹⁰⁷ is independently selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. k is an integer from 0 to 20 or 1 to 20; k′″ is an integer from 0 to 20. X¹⁰¹ to X¹⁰⁸ is selected from C (including CH) or N. Z¹⁰¹ and Z¹⁰² is selected from NR¹⁰¹, O, or S.

Non-limiting examples of the additional host materials that may be used in an OLED in combination with the host compound disclosed herein are exemplified below together with references that disclose those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, US7154114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472,

Emitter:

An emitter example is not particularly limited, and any compound may be used as long as the compound is typically used as an emitter material. Examples of suitable emitter materials include, but are not limited to, compounds which can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as B-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.

Non-limiting examples of the emitter materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, US06699599, US06916554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670, US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, US20080233410, US20080261076, US20080297033, US200805851, US2008161567, US2008210930, US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663, US20100244004, US20100295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559, US20110108822, US20110204333, US2011215710, US2011227049, US2011285275, US2012292601, US20130146848, US2013033172, US2013165653, US2013181190, US2013334521, US20140246656, US2014103305, US6303238, US6413656, US6653654, US6670645, US6687266, US6835469, US6921915, US7279704, US7332232, US7378162, US7534505, US7675228, US7728137, US7740957, US7759489, US7951947, US8067099, US8592586, US8871361, WO06081973, WO06121811, WO07018067, WO07108362, WO07115970, WO07115981, WO08035571, WO2002015645, WO2003040257, WO2005019373, WO2006056418, WO2008054584, WO2008078800, WO2008096609, WO2008101842, WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO2011044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO2013174471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450,

HBL:

A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and or higher triplet energy than one or more of the hosts closest to the HBL interface.

In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.

In another aspect, compound used in HBL contains at least one of the following groups in the molecule:

wherein k is an integer from 1 to 20; L¹⁰¹ is an another ligand, k′ is an integer from 1 to 3. ETL:

Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.

In one aspect, compound used in ETL contains at least one of the following groups in the molecule:

wherein R¹⁰¹ is selected from the group consisting of hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. Ar¹ to Ar³ has the similar definition as Ar's mentioned above. k is an integer from 1 to 20. X¹⁰¹ to X¹⁰⁸ is selected from C (including CH) or N.

In another aspect, the metal complexes used in ETL include, but are not limited to the following general formula:

wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L¹⁰¹ is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.

Non-limiting examples of the ETL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR01117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,

Charge Generation Layer (CGL)

In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers.

In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also encompass undeuterated, partially deuterated, and fully deuterated versions thereof.

EXPERIMENTAL Synthesis of Tetrabenzoazonine Synthesis of 2′-bromo-[1,1′-biphenyl]-2-amine

A dimethylacetamide (DMA) (150 mL) and water (75 mL) mixture was bubbled with nitrogen gas for 15 min., followed by an addition of 2-iodoaniline (10.0 g, 45.7 mmol), (2-bromophenyl)boronic acid (13.7 g, 68.5 mmol), sodium bicarbonate (15.3 g, 182.6 mmol), and tetrakis(triphenylphosphine)palladium(0) (2.6 g, 2.3 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with dichloromethane (DCM). The solvent was removed in vacuo and the residue was purified by flash column chromatography using 10% ethyl acetate (EA) in hexane to afford 2′-bromo-[1,1′-biphenyl]-2-amine (7.3 g, 64% yield) as yellow oil.

Synthesis of N-([1,1′-biphenyl]-2-yl)-2′-bromo-[1,1′-biphenyl]-2-amine

Toluene (100 mL) was bubbled with nitrogen gas for 15 min., followed by an addition of triphenylphosphine (1.1 g, 4.0 mmol) and palladium acetate (226 mg, 1.0 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min., then 2′-bromo-[1,1′-biphenyl]-2-amine (2.5 g, 10.1 mmol), 2-iodo-1,1′-biphenyl (4.2 g, 15.1 mmol), and sodium tert-butoxide (1.5 g, 15.1 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using 10% DCM in hexane to afford N-([1,1′-biphenyl]-2-yl)-2′-bromo-[1,1′-biphenyl]-2-amine (2.4 g, 60% yield) as colorless oil.

Synthesis of 5-(2′-bromo-[1,1′-biphenyl]-2-yl)dibenzo[c,e][1,2]azaborinin-6(5H)-ol

1,2-Dichlorobenzene (7 mL) was bubbled with nitrogen gas for 15 min., followed by an addition of N-([1,1′-biphenyl]-2-yl)-2′-bromo-[1,1′-biphenyl]-2-amine (761 mg, 1.9 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min., then boron tribromide (BBr₃) (IM solution in DCM, 2.1 m, 2.1 mmol) was added and the mixture was heated to reflux for 18 hours. After cooling (˜22° C.), the reaction mixture was concentrated in vacuo. The residue was purified by flash column chromatography using 20-40% DCM in hexane to 5-(2′-bromo-[1,1′-biphenyl]-2-yl)dibenzo[c,e][1,2]azaborinin-6(5H)-ol (577 mg, 71% yield) as a white powder.

Synthesis of 9H-tetrabenzo[b,d,f,h]azonine

A dimethoxyethane (DME) (12 mL) and water (4 mL) mixture was bubbled with nitrogen gas for 30 min., followed by an addition of tetrakis(triphenylphosphine)palladium(0) (29 mg, 0.025 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min., then 5-(2′-bromo-[1,1′-biphenyl]-2-yl)dibenzo[c,e][1,2]azaborinin-6(5H)-ol (185 mg, 0.43 mmol) and K₂CO₃ (150 mg, 1.1 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was extracted by DCM. The extracts were dried over MgSO₄ and the solvent was removed in vacuo. The residue was purified by flash column chromatography using 5-10% DCM in hexane (containing 0.25% triethylamine) to afford 9H-tetrabenzo[b,d,f,h]azonine (52 mg, 38% yield) as a white solid.

Synthesis of Compound III-a-1

o-Xylene (3 mL) was bubbled with nitrogen gas for 10 min., followed by an addition of tris(dibenzylideneacetone)dipalladium(0) (Pd₂(dba)₃) (29 mg, 0.031 mmol) and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (514 mg, 0.13 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min., then 9H-tetrabenzo[b,d,f,h]azonine (100 mg, 0.31 mmol), iodobenzene (256 mg, 1.3 mmol), and sodium tert-butoxide (451 mg, 0.47 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using hexane to 10% DCM in hexane to afford Compound III-a-1 (55 mg, 44% yield) as a white solid.

Synthesis of Compound III-a-5

o-Xylene (40 mL) was bubbled with nitrogen gas for 10 min., followed by the addition of Pd₂(dba)₃ (2.2 g, 2.3 mmol) and tri-ter-butylphosphine (1.9 g, 9.4 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min., then 9H-tetrabenzo[b,d,f,h]azonine (2.5 g, 7.8 mmol), 3-iodo-9-phenyl-9H-carbazole (5.8 g, 15.7 mmol), and sodium tert-butoxide (978 mg, 10.2 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using hexane to 30% DCM in hexane to afford Compound III-a-5 (2.5 g, 57% yield) as an off-white solid.

Synthesis of Compound III-a-21

o-Xylene (2.5 mL) was bubbled with nitrogen gas for 10 min., followed by an addition of Pd₂(dba)₃ (60 mg, 0.065 mmol), and tri-tert-butylphosphine (107 mg, 0.26 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min., then 9H-tetrabenzo[b,d,f,h]azonine (250 mg, 0.78 mmol), 2-bromotetraphenylene (100 mg, 0.26 mmol), and sodium ten-butoxide (63 mg. 0.65 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling, the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using hexane to 30% DCM in hexane to afford Compound III-a-21 as an off-white solid.

Synthesis of 9-(3-iodophenyl)-9H-carbazole

m-Xylene (250 mL) was bubbled with nitrogen gas for 10 min., followed by the addition of 1,3-diiodobenzene (19.7 g, 59.8 mmol), carbazole (5.0 g, 29.9 mmol), potassium carbonate (20.7 g, 150.0 mmol), 18-crown-6 (7.9 g, 29.9 mmol), and copper (1.9 g, 29.9 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using hexane to DCM to afford 9-(3-iodophenyl)-9H-carbazole (5.7 g, 52% yield) as an off-white solid.

Synthesis of Compound III-a-22

o-Xylene (35 mL) was bubbled with nitrogen gas for 10 min., followed by the addition of Pd₂(dba)₃ (602 mg, 0.66 mmol) and 2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl (1.2 g, 2.6 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min., then 9H-tetrabenzo[b,d,f,h]azonine (2.1 g, 6.6 mmol), 9-(3-iodophenyl)-9H-carbazole (3.2 g, 8.6 mmol), and sodium tert-butoxide (948 mg, 9.9 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using hexane to 30% DCM in hexane to afford Compound III-a-22 (1.9 g, 52% yield) as a white solid.

Synthesis of 6-bromo-9H-tetrabenzo[b,d,f,h]azonine and 6,12-dibromo-9H-tetrabenzo[b,d,f,h]azonine

A mixture of 9H-tetrabenzo[b,d,f,h]azonine (4.0 g, 12.5 mmol) and 2-bromocyclopentane-1,3-dione (4.4 g, 25.1 mmol) in THF (110 ml) was stirred for 4 hours. The solvent was removed in vacuo and the residue was partitioned between water and DCM. The organic layer was separated and removed in vacuo and the residue was purified by flash column chromatography using hexane to 30% DCM in hexane to afford an inseparable mixture of 6-bromo-9H-tetrabenzo[b,d,f,h]azonine and 6,12-dibromo-9H-tetrabenzo[b,d,f,h]azonine (7.3 g).

Synthesis of 6-(dibenzo[b,d]furan-4-yl)-9H-tetrabenzo[b,d,f,h]azonine and 6,12-bis(dibenzo[b,d]furan-4-yl)-9H-tetrabenzo[b,d,f,h]azonine

Toluene (120 mL), ethanol (10 mL), and water (12 mL) were bubbled with nitrogen gas for 10 min., followed by the addition of Pd₂(dba)₃ (1.7 g 1.8 mmol) and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (3.0 g, 7.4 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min., then an inseparable mixture of 6-bromo-9H-tetrabenzo[b,d,f,h]azonine, 6,12-dibromo-9H-tetrabenzo[b,d,f,h]azonine (7.3 g), dibenzo[b,d]furan-4-ylboronic acid (9.7 g, 45.9 mmol), and potassium phosphate tribasic (11.7 g, 55.1 mmol) was added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using hexane to 10% EA in hexane to afford 6-(dibenzo[b,d]furan-4-yl)-9H-tetrabenzo[b,d,f,h]azonine (2.2 g) and 6,12-bis(dibenzo[b,d]furan-4-yl)-9H-tetrabenzo[b,d,f,h]azonine (4.0 g).

Synthesis of Compound III-b-5

o-Xylene (20 mL) was bubbled with nitrogen gas for 10 min., followed by the addition of Pd₂(dba)₃ (358 mg, 0.39 mmol) and 2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl (730 mg, 1.6 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min., then 6-(dibenzo[b,d]furan-4-yl)-9H-tetrabenzo[b,d,f,h]azonine (1.9 g, 3.9 mmol), iodobenzene (3.2 g 15.7 mmol), and sodium tert-butoxide (564 mg, 5.9 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using hexane to 30% DCM in hexane to afford 6-(dibenzo[b,d]furan-4-yl)-9-phenyl-9H-tetrabenzo[b,d,f,h] Compound III-b-5 (1.8 g, 82% yield) as a pale yellow solid.

Synthesis of Compound III-b-18

o-Xylene (40 mL) was bubbled with nitrogen gas for 10 min., followed by the addition of Pd₂(dba)₃ (351 mg, 0.38 mmol) and 2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl (716 mg, 1.5 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min., then 6,12-bis(dibenzo[b,d]furan-4-yl)-9H-tetrabenzo[b,d,f,h]azonine (2.5 g, 3.8 mmol), iodobenzene (3.1 g, 15.3 mmol), and sodium tert-butoxide (479 mg, 5.0 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using hexane to 10% EA in hexane to afford Compound III-b-18 as a pale yellow solid.

Synthesis of Compound V-31-2

o-Xylene (1.5 mL) was bubbled with nitrogen gas for 10 min., followed by the addition of 2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl (29 mg, 0.061 mmol) and Pd₂(dba)₃ (14 mg, 0.15 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min., then 3-iodobenzonitrile (70 mg, 0.31 mmol), 6,12-bis(dibenzo[b,d]furan-4-yl)-9H-tetrabenzo[b,d,f,h]azonine (100 mg, 0.15 mmol), and sodium tert-butoxide (19 mg, 0.20 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using 10-30% EA in hexane to afford Compound V-31-2 (13 mg, 11% yield) as a pale yellow solid.

Synthesis of Compound V-32-1

o-Xylene (30 mL) was bubbled with nitrogen gas for 10 min., followed by the addition of 2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl (1.2 g, 2.5 mmol) and Pd₂(dba)₃ (573 mg, 0.63 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min., then 3,5-diiodobenzonitrile (500 mg, 1.4 mmol), 9H-tetrabenzo[b,d,f,h]azonine (1.0 g, 3.1 mmol), and sodium tert-butoxide (451 mg, 4.7 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using 10-30% EA in hexane to afford Compound V-32-1 (189 mg, 8% yield) as a pale yellow solid.

Synthesis of Compound III-a-6

Toluene (100 mL) was bubbled with nitrogen gas for 15 min., followed by the addition of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (2.1 g, 5.1 mmol) and Pd₂(dba)₃ (1.1 g, 1.2 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min., then 2-iododibenzo[b,d]furan (5.3 g, 18.0 mmol), 9H-tetrabenzo[b,d,f,h]azonine (4.0 g, 12.5 mmol), and sodium tert-butoxide (1.7 g, 17.7 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using 10% DCM in hexane to afford Compound III-a-6 (4.6 g, 76% yield) as a white solid.

Synthesis of Compound III-a-23

Toluene (100 mL) was bubbled with nitrogen gas for 15 min., followed by the addition of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (1.0 g, 2.4 mmol) and Pd₂(dba)₃ (0.60 g, 0.66 mmol). The mixture was bubbled with nitrogen gas for 15 min., then 4-(3′-iodo-[1,1′-biphenyl]-3-yl)dibenzo[b,d]thiophene (4.1 g, 8.9 mmol), 9H-tetrabenzo[b,d,f,h]azonine (2.0 g, 6.3 mmol), and sodium tert-butoxide (0.80 g, 8.3 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using 10-20% DCM in hexane to afford Compound III-a-23 (3.5 g. 85% yield) as a white solid.

Synthesis of Compound II-3

Toluene (60 mL) was bubbled with nitrogen gas for 15 min., followed by the addition of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (2.0 g, 4.9 mmol) and Pd₂(dba)₃ (1.1 g, 1.2 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min., then 4,4′-diiodo-1,1′-biphenyl (2.4 g, 5.9 mmol), 9H-tetrabenzo[b,d,f,h]azonine (3.8 g, 11.9 mmol), and sodium tert-butoxide (1.6 g, 16.7 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using 10-20% DCM in hexane to afford Compound II-3 (4.5 g, 97% yield) as a white solid.

Synthesis of Compound III-a-9

Toluene (3 mL) was bubbled with nitrogen gas for 10 min., followed by the addition of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (30 mg, 0.073 mmol) and Pd₂(dba)₃ (20 mg, 0.022 mmol). The mixture was bubbled with nitrogen gas for 15 min., then 4-iododibenzo[b,d]thiophene (78 mg, 0.25 mmol), 9H-tetrabenzo[b,d,f,h]azonine (58 mg, 0.18 mmol), and sodium tert-butoxide (70 mg, 0.73 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed In vacuo and the residue was purified by flash column chromatography using 10% DCM in hexane to afford Compound III-a-9 as a white solid.

Synthesis of Compound II-6

Toluene (4 mL) was bubbled with nitrogen gas for 10 min., followed by an addition of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (66 mg, 0.16 mmol) and Pd₂(dba)₃ (32 mg, 0.035 mmol). The mixture was bubbled with nitrogen gas for 15 min., then 2,8-diiododibenzo[b,d]furan (85 mg, 0.20 mmol), 9H-tetrabenzo[b,d,f,h]azonine (129 mg, 0.40 mmol), and sodium tert-butoxide (54 mg, 0.56 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using 10% DCM in hexane to afford Compound II-6 (187 mg, 52% yield) as a white solid.

Synthesis of Compound V-31-1

Toluene (3 mL) was bubbled with nitrogen gas for 10 min., followed by an addition of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (43 mg, 0.11 mmol) and Pd₂(dba)₃ (21 mg, 0.023 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min., then 3-iodobenzonitrile (81 mg, 1.4 mmol), 9H-tetrabenzo[b,d,f,h]azonine (81 mg, 0.25 mmol), and sodium tert-butoxide (34 mg, 0.35 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using 10-40% DCM in hexane to afford Compound V-31-1 (53 mg, 50% yield) as a white solid.

Synthesis of Compound V-33-1

Toluene (3 mL) was bubbled with nitrogen gas for 10 min., followed by an addition of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (54 mg, 0.13 mmol) and Pd₂(dba)₃ (29 mg, 0.032 mmol). The mixture was bubbled with nitrogen gas for 15 min., then 4-iodobenzonitrile (106 mg, 0.46 mmol), 9H-tetrabenzo[b,d,f,h]azonine (100 mg, 0.31 mmol), and sodium tert-butoxide (42 mg, 0.44 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using 10-40% DCM in hexane to afford Compound V-33-1 (86 mg, 65% yield) as a white solid.

Synthesis of Compound V-34-1

Toluene (3 mL) was bubbled with nitrogen gas for 10 min., followed by the addition of 2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl (234 mg, 0.50 mmol) and Pd₂(dba)₃ (128 mg, 0.14 mmol). The resulting mixture was bubbled with nitrogen gas for 15 min., then 4-iodophthalonitrile (446 mg, 1.8 mmol), 9H-tetrabenzo[b,d,f,h]azonine (400 mg, 1.3 mmol), and sodium tert-butoxide (169 mg, 1.8 mmol) were added. The mixture was bubbled with nitrogen gas for 15 min. and refluxed for 18 hours. After cooling (˜22° C.), the reaction mixture was filtered through a silica pad and washed with toluene. The solvent was removed in vacuo and the residue was purified by flash column chromatography using 10-40% DCM in hexane to afford Compound V-34-1 (150 mg, 27% yield) as an off-white solid.

Photophysics and Electrochemistry Results

Experimentally, tetrabenzoazonine

shows singlet and triplet energy of 359 nm and 410 nm respectively, confirming the high triplet nature. Cyclic voltammetry shows E_(ox)=0.91 (IR) and E_(red)=3.00 (R). Additional Photophysics and electrochemistry data are summarized in FIG. 3.

The data in FIG. 3 shows compounds of Formula I are suitable for many application in OLED. For example, Compound II-3 has HOMO/LUMO levels suitable for use as a hole transporter. Compounds of the III-a series have high triplet energies and are suitable as hosts for blue phosphorescent OLED. Compounds of the III-b series have triplet energies suitable as hosts for green and yellow phosphorescent OLED. Compounds of the III-a and III-b series are also suitable as charge blocking (hole or electron blocking) layer materials. Compounds of the V series are suitable as delayed fluorescence emitters as exemplified by the small energy difference between triplet and singlet, and the high PLQY from presumably the charge transfer emission at room temperature.

DEVICE EXAMPLES

In the OLED experiment, all device examples were fabricated by high vacuum (<10⁻⁷ Torr) thermal evaporation. The anode electrode is ˜800 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of LiF followed by 1,000 Å of Al. All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H₂O and O₂) and a moisture getter was incorporated inside the package.

Device Example 1

The organic stack of the Device Examples in Table I consists of sequentially, from the ITO surface, 100 Å of LG101 (purchased from L.G Chem, Korea) as the hole injection layer (HIL), 250 Å of Compound A the hole transport layer (HTL), 50 Å of Compound III-a-5 as the secondary hole transport layer (also known as electron blocking layer), 300 Å of Compound B doped with 20% of the emitter Compound C as the emissive layer (EML), 50 Å of Compound B as ETL2 and 300 Å of Alq₃ as ETL1. At 1000 cd/m², the device efficiency was 17% EQE with CIE of 0.169, 0.387. The result demonstrated that Compounds of Formula I are suitable for OLED applications.

It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting. 

We claim:
 1. A compound having a structure of Formula I:

wherein each one of X¹ to¹⁶ is independently CR^(X) or N; wherein each R^(X) and R are independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof; and wherein any adjacent R^(X) can join to form fused or unfused rings.
 2. The compound of claim 1, having the structure of Formula I-a:

wherein each one of R¹ to R¹⁶ independently represents a substituent selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof, wherein any adjacent R¹-R¹⁶ can join to form a fused or unfused ring.
 3. The compound of claim 2, having the structure of Formula II:

wherein n is an integer ≥1; wherein R^(t) is

wherein all rings are optionally independently substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof; and wherein any adjacent substituents can join to form fused or unfused rings.
 4. The compound of claim 2, wherein R is selected from the group consisting of aryl, heteroaryl, substituted aryl, and substituted heteroaryl.
 5. The compound of claim 2, wherein at least one of R¹ to R¹⁶ is selected from the group consisting of aryl, heteroaryl, substituted aryl, and substituted heteroaryl.
 6. The compound of claim 2, wherein R is a triarylamine containing group.
 7. The compound of claim 2, wherein R is a group containing at least one electron withdrawing group of CN, F, C_(m)F_(2m+1), Si_(m)F_(2m+1), NCO, NCS, OCN, SCN, OC_(m)F_(2m+1), or SC_(m)F_(2m+1), wherein m≥1.
 8. The compound of claim 7, wherein the compound is selected from the group consisting of:

wherein R^(e) is CN, F, C_(m)F_(2m+1), Si_(m)F_(2m+1), NCO, NCS, OCN, SCN, OC_(m)F_(2m+1), or SC_(m)F_(2m+1), and m≥1; and wherein R^(t) is

wherein all rings of R^(t) are optionally independently substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof; and wherein any adjacent substituents on R^(t) can join to form fused or unfused rings.
 9. The compound of claim 2, wherein R is a group containing pyrimidine or triazene.
 10. The compound of claim 1, wherein at least one of X¹ to X¹⁶ is N.
 11. The compound of claim 1, wherein at least two of adjacent R¹-R¹⁶ are fused into

wherein Z is CR′R″, NR′, O, S, or Se; wherein R′ and R″ are independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof; and wherein all of the rings are optionally substituted.
 12. A first organic light emitting device comprising: an anode; a cathode; and an organic layer, disposed between the anode and the cathode, comprising a compound having a structure of Formula I:

wherein each one of X¹ to X¹⁶ is independently CR^(X) or N; wherein R^(X) and R are independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof; and wherein any adjacent R^(X) can join to form fused or unfused rings.
 13. The first organic light emitting device of claim 12, wherein the organic layer is an emissive layer and the compound of Formula I is a host.
 14. The first organic light emitting device of claim 12, wherein the organic layer further comprises a phosphorescent emissive dopant wherein the phosphorescent emissive dopant is a transition metal complex having at least one ligand or part of the ligand if the ligand is more than bidentate, selected from the group consisting of:

wherein each X¹ to X¹³ are independently selected from the group consisting of carbon and nitrogen; wherein X is selected from the group consisting of BR′, NR′, PR′, O, S, Se, C═O, S═O, SO₂, CR′R″, SiR′R″, and GeR′R″; wherein R′ and R″ are optionally fused or joined to form a ring; wherein each R_(a), R_(b), R_(c), and R_(d) may represent from mono substitution to the possible maximum number of substitution, or no substitution; wherein R′, R″, R_(a), R_(b), R_(c), and R_(d) are each independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and wherein any two adjacent substituents of R_(a), R_(b), R_(c), and R_(d) are optionally fused or joined to form a ring or form a multidentate ligand.
 15. The first organic light emitting device of claim 12, wherein the organic light emitting device is incorporated into a device selected from the group consisting of a consumer product, an electronic component module, an organic light-emitting device, and a lighting panel.
 16. The first organic light emitting device of claim 12, wherein the organic layer is an emissive layer and the compound having structure according to Formula I is a first light emitting compound.
 17. The first organic light emitting device of claim 16, wherein the first organic light emitting device emits a luminescent radiation at room temperature when a voltage is applied across the organic light emitting device; and wherein the luminescent radiation comprises a delayed fluorescence process.
 18. The compound of claim 1, wherein the compound is selected from the group consisting of:

wherein all of the rings are optionally substituted, and

wherein R^(t) is

wherein all rings of R^(t) are optionally independently substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, azadibenzofuran, azadibenzothiophene, azadibenzoselenophene, triphenylene, azatriphenylene, and combinations thereof; and wherein any adjacent substituents on R^(t) can join to form fused or unfused rings.
 19. The compound of claim 10, wherein the compound is selected from the group consisting of:

wherein all of the rings are optionally substituted. 